Vat and sulphur dyestuff preparation



UNITED STATES PATENT OFFICE VAT AND SULPHUR DYESTUFF PREPARATION Hermann Berthold, Leverkusen-I. G. Work-onthe-Rhine, Germany,"assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application December 14, 1931, Serial No. 581,071. In Germany December 19,

.1930 a 20 Claims. (on. 8-6) The present invention relates to new vat and u omarily empl y d in vat dy i and in e Sulphur dyestuff preparations suitable for printpresence of an alkali, such as caustic soda soluing purposes and to a process of printing textile on, caustic Potash y Preferably a Weaker fibers with these preparations, alkali, such as ammonia, sodium carbonate po- In accordance with the invention beta-aryltassium carbonate or the like. As reducing 5 sulphamino anthraquinones or substitution agents alkali metal hydrosulphites are preferred, products thereof, or also reduction products of but other reducin a n u s ta i these substances which still contain oxygen in chloride etc. are likewise operab e. A e W the meso-position, or mixtures of compounds of p minoa th aq no a reduction P 10 these types are employed to influence favorably uct thereof containing oxygen in the meso-posithe capacity for printing f vat or sulphur dyetion is added to the preparations above menstufls, that is, to improve the strength of the tioned at any desired stage of their manufacl rintings obtainable and at the same time the ture. The dyestufi pastes thus obtainable conv speed of fixation. taining the dyestuff in a reduced form (in the The further addition of anthraquinone, hycase of applying a rather weak alkali, such as droxyanthraquinones, aminoanthraquinones, anammonia, Soda P probably in the form thraquinone-sulphonic or carboxylic acids or rehe ee lelleo a d) d likewise t d p duction products of these compounds containing do not congeal, do not form crusts, and for printoxygen in the meso-position or salts of said comng pu p s, p ss ss s mi a advan as t pounds, still enhances the eflicacy of the first P pa tions mentioned before. 20 mentioned products in many cases. Suitable beta-arylsulphamino-anthraquinones The beta-arylsulphamino-anthraquinones, and r a p those obtainable by condensing also the other anthraquinone derivatives or beta-aminoanthraquinone, 2.6-diaminoanthrathe reduction products of the same containing quinone, 2.7-diaminoanthraquinone etc. with oxygen in the mesa-position are preferably apbenzene sulphochloride, naphthalene sulphochlo- 25 plied in a finely divided state for the purposes ides, h lO ll S thereof, 511011 88 0113110, meta of the present process. This may be accom- D -to n sulpheehlelide, xylene p plished in a variety of, ways. Thus, for examo ides c Dle, the substances in question may be finely The beta-arylsulphaminoanthraquinones in ground or they may be dissolved in sulphuric question c r po example, to the 30 acid and reprecipitated with water. mullet- The incorporating of the beta-arylsulphamino o anthraquinones or their reduction products con- II taining oxygen in the mesa-position with the C C vat or sulphur dyestuffs may be accomplished in a variety of ways. For example, the different constituents may be mixed in the dry state or in form of aqueous pastes; or the beta-arylsulphaminoanthraquinones etc. may be added to 40 the printing colors at any stage of their manufacture. The best resultsare generally obtained when adding the compounds in question to aqueous pastes of the dyestufis containing glycerine, ODEHN or another suitable polyvalent water soluble al- 0 cohol, such as ethylene-glycol, diethyleneglycol, l

thiodiglycol, thiodiglycerol and the like. The pastes thus obtainable are very stable, do not etc. Salt formation of these compounds takes deposit or dry up, do not form crusts and can be place at the nitrogen atoms. Obviously, instead I applied for printing purposes even after proof the free arylsulphaminoanthraquinones them 5o longed storing. In some cases it will be 'of adselves salts thereof, especially alkali metal salts 5 vantage to work in the following manner: The (including the ammonium salts) may be applied, dyestufi is suspended in water, glycerine or anwhich salts are to be considered equivalents. to other water soluble polyvalent alcohol as menthe free arylsulphaminoanthraquinones. tioned above is added, and the dyestufi, reduced Besides the beta-arylsulphaminoanthraquim,

in this suspension by means of a reducing agent ones and/or theirreductlon product: above spei 17 v fied, so-called hydrotropic agents may be added. By the term hydrotropic agents" is understood compounds promoting the solubility of water insoluble or diflicultly soluble substances in water (compare Neuberg, Biochemische Zeitschrift vol. 76, (1916) page 107 11.; Tamba, Biochemische Zeitschrift vol. 145, (1924) page 415 11.; Neuberg, Sitzungsberichte der konigl. preuss. Akademie der Wissensch. 1916). Suitable hydrotropic agents are for example:-urea, substituted ureas, 'thiourea, hexamethylene-tetramine, the potassium salt of ethylether sulphonic acid or -methylether sulphonic acid, the ammonium or alkali metal salts of the following acidsz-phenylacetic acid, benroic acid, salicylic acid, the benzene sulphinic acids, the benzene sulphonic acids, the para-toluene sulphonic acid, naphthalene sulphonic acids, for example, naphthalene-lor -2-sulphonic acid, aniline sulphonic acids and substitution products thereof, such as for example, dimethyl-nietanilicor dietliylmetanilic acid, dimethyl-i-aminoben- .in other cases, mainly zoic acid, alkali metal salts of hydroaromatic carboxylicandsulphonic acids, as for example, the cyclohexane carboxylic acid, tetra-hydronaphthalenebeta-sulphonic acid and the like.

It may be mentioned that the hydrotropic agent yielding the best resultin a particular case will depend on the nature of the dyestuif to be printed as well as on the printing method applied.

For printing purposes the preparations described above are worked up to printing colors in any desired manner. For example, the dry preparations may be made up to aqueous pastes suitably in the presence of glycerine, ethylene glycol or another suitable polyvalent water soluble alcohol, a thickening of any desired composition is added, furthermore, caustic soda solution and sodium hydrosulphite, and the mixture is heated to 60 0., until the dyestuif has dissolved in the form of its leucr derivative. After cooling, sodium formaldehydesulphoxylate and potassium carbonate-are stirred into the mixture. Cotton or another suitable textile product is printed with this printing color, the printings are steamed, for example, in a Mather-Flatt apparatus and developed by a treatment with suitable oxidizing agents, such as oxygen (air), p0- tassium bichromate and acetic acid and the like. Finally theprintings are soaped while boiling.

Another method of printing with 'my preparations will be as follows:-

The powdery preparations are made .up' to an aqueous paste, a thickening, glycerine, potassium carbonate and sodium formaldehydesulphoxylate are added and textile products are printed with these printing colors containing the dyestufl in the unreduced state. The printings are steamed, whereby reduction of the dyestuff occurs, and further treated as described above. Instead of the powdery preparations the aqueous pastes thereof, which may contain glycerine, ethylene glycol, diethylene glycol, thiodiglycerol etc. may be applied, whereby in case that the pastes contain glycerine etc., a further addition of the latter when preparing the printing colors willbeunnecessaryinmanycisesbutnecessary depending on the 'type of the dyestuif applied. According to this process also my dyestuif preparations,.obtained by reducing the. dyestuffs in the presence of water; glycerine-and an alkali, preferably one which is weaker than caustic alkali solutions, such as ammonia, sodium carbonate, potassium carbonate etc., may be worked up to printing colors and applied for printing purposes; It maybe meationed that also in thiscase the addition of a suitable reducing agent such as sodium formhldehyde sulphoxylate and of an alkali and in most cases of glycerine, thiodiglycol or the like, to the printing color will-be necessary or at least advantageous in order to obtain the best results.

When using in the claims the term vat or sulphur dyestuif preparations for printing purposes the same is intended to include not only the dry dyestuif preparations of vat or sulphur dyestuffs as defined before, but also the corresponding printing colors or aqueous pastes of the dyestufl's with or without the addition of glycerine or other water soluble polyvalentalcohols, alkalies, reducing agents etc.

The following examples will illustrate the invention, without limiting it thereto, the parts being by weight:--

Example 1 :A printing paste is prepared from 20 parts of a 10% aqueous paste of 6.6'-diethoxy- 2-B'-bisthionaphtheneindigo with the addition of 7 parts of glycerine, 1 part of 2-para-toluene sulphaminoanthraquinoneor2.6-di-para-toluenesulphaminoanthraquinone (most finely ground) and 72 parts of a thickening containing in 1000 parts Parts Wheat starch 60 Water 4 1 British gum powder-"n, 60 Industrial gum 1:1 260 Tragacanth 6551000 Potassium carbonate 150 Sodium formaldehyde sulphoxylate; 150

This printing color prints considerably better.

and yields printings, which fix better and are of greater strength than the printings obtainable by the same printing color but without the addition of the para-toluene-sulphaminoanthra-- quinone -or 2.6-di-para-toluene-sulphaminoanthraquinone. Valuable results are likewise obtained, in case the anthraquinone derivative is added to the dry dyestufl. in a flnely ground form with or without the addition of emulsifying agents or hydrotropic agents, or when the dyestuil' is applied in form of a press cake or when the same is previously reduced by means of sodium hydrosulphite in the presence of water, glycerine or another similar water soluble polyvalent alcohol and ammonia".

Example 2:-The dyestuif of Example 1 may be replaced by the following dyestufl's:.

(1) The dyestuff from 6-methoxy-3-hydroxythionaphthene and 4-methyl-8-bromo-2.3 -dihydro-3-keto thionaphthene-2- (para-dimethylamino) -anil;

(2) The carbazole from 5.5'-dibenzoyldiamino- 1.1'-dianthraquinonylamine;

(3) The carbazole from 4.5'-dibenzoyldiamino- 1.1'-dianthraquinonylamine;

(4) The carbazole from 4.5'-dibenzoylamino- 8'-methoxy-1.1'-dianthraquinonylamine;

(5) The dyestuif obtainable by oxidizing naphthooxythiophencarboxylic acid with potassium' ferric cyanide in alkaline solution;

(6) 6.8'-dichloro 4.4K- dimethyl-bis-thionaphthene-indigo; 0

(7) 2.7-dibromoanthanthrone, (8) Brominated pyranthrone, (9) Alpha-isophthaloylaminoanthraquinone,

(10) 5.5'-dibenzoyldiamino-1.1-dianthraquinonyloxamide,

(11) The dyestuif enumerated in Colour Index 1st. ed. under No. 9.6!).

These dyestuffs likewise yield stronger prints and fix better, when printed in the presence of an arylsulphamino-anthraquinone than in the absence of such compound.

Instead of the arylsulphaminoanthraquinones mentioned in Example 1, beta-phenylsulphamino-anthraquinone, 2.6-diphenylsulphaminoanthraquinone,- beta xylylsulphaminoanthraquinones, 2.7-di-ortho-, -metaor -para-tolylsulphaminoanthraquinone, alphaor beta-naphthylsulphamino-anthraquinone etc. or salts of these compounds, such as the sodiumpotassiumor ammonium salts may be applied with a similar effect.

It may be mentioned that as far as sulphur dyestuffs are concerned the best results are generally obtained when applying sulphur dyestuffs, which also without the addition of arylsulphaminoanthraquinones possess afiinity to textile fibers in printing processes.

The above preparations yield especially good results in cotton printing, but,may likewise be applied in the printing or slop-"padding of other textile materials such as viscose, wool, silk, acetate silk mixed fabrices and the like.

I claim:-

1. Vat and sulphur dyestuif printing preparations foruse on textile fibers comprising as a printing assistant a compound of the group consisting of beta-arylsulphamino-anthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the meso-position. v

2. Vat and sulphur dyestufi printing preparations for use on textile fibers comprising a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-arylsulphamino-anthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the mesoposition.

3. Vat and sulphur dyestuif printing preparations for use on textile fibers comprising a water soluble polyvalent alcohol and as a printing assistant a compound of the group consisting of beta-arylsulphamino anthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the meso-position.

4. Vat and sulphur dyestuif printing preparations for use on textile fibers comprising a water soluble polyvalent alcohol, a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-arylsulphamino-anthraquinones, substituti on products thereof and such reduction products of these'compounds as still contain oxygen in the meso-position.

5. Vat and sulphur dyestuif printing preparations for use on textile fibers comprising as a printing assistant a compound of the group consisting of beta-phenylsulphaminoanthraquinones, which may be substituted in the benzene nucleus by alkyl groups, and such reduction products of these compounds as still contain oxygen in the meso-positiori.

6. Vat and sulphur dyestufi printing preparations for use on textile fibers comprising a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-phenylsulphamino-anthraquinones, which may be substituted in the benzene nucleus by alkyl groups, and such reduction products of these compounds as still contain oxygen in the meso-position.

7. Vet and sulphur dyestuff printing preparations for use on textile fibers comprising a water soluble polyvalent alcohol and as a printing assistant a compound of the' group consisting of beta phenylsulphaminoanthraquinones, which may be substituted in the benzene nucleus by alkyl groups and such reduction products of these compounds as still contain oxygen in the mesoposition.

8. Vat and sulphur dyestuff printing preparations for use on textile fibers comprising a water soluble polyvalent alcohol, a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-phenylsulpaminoanthraquinones, which maybe, substituted in the benzene nucleus by alkyl groups, and such reduction products of these compounds as still contain oxygen in the meso-position.

9. Vat and sulphur dyestuif printing preparations for use on textile fibers comprising glyc erinel a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-arylsulphamino-anthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the mesa-position.

10. Vat and sulphur dyestufi printing preparations for use on textile fibers comprising glycerine, a hydrotropic agent and as a printing assistant a compound of the group consisting of beta-phenylsulphamino anthraquinones, which may be substituted in the benzene nucleus by alkyl groups, and such reduction products of these compounds as still contain oxygen in the mesoposition.

11. A vat dyestufi printing preparation for use on textile fiberscomprising 5.5-dibenzoyldiamino 1.1' dianthraquinonylamine carbazole, glycerine and as a printing assistant 2. compound of the group consisting of Z-para-toluene-sulphaminoanthraquinone and 2.6-di-para-toluenesulphaminoanthraquinone.

12. A vat dyestufi printing preparation for use on textile fibers comprising 6.6'-diethoxy-2.2'-bisthionaphthene indigo, glycerine and as a printing assistant a compound of the group consisting of 2-para-toluene-sulphaminoanthraquinone and 2.6 di para-toluene sulphaminoanthraquinone.

13. The process which comprises printing textile fibers with printing colors derived from dyestuffs of the group consisting of vat and sulphur dyestuffs, said colors containing as a printing assistant a compound of the group consisting of aryl-sulphaminoanthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the meso-position.

14. The process which comprises printing textile fibers with printing colors derived from dyestuffs of the group consisting of vat and sulphur dyestuffs, said colors containing a hydrotropic agent and as a printing assistant a compound of the group consisting of arylsulphaminoanthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the meso-position.

15. The process which comprises printing textile fibers with printing colors derived from dyestuffs of the group consisting of vat and sulphur dyestuffs, said colors containing a water soluble polyvalent alcohol and as a printing assistant a compound of the group consisting of arylsulphaminoanthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen'in the meso-position. I

16. The process which comprises printing textile fibers with printing colors derived from dyestuffs of the group consisting o1 vat and sulphur dyestuiis, said colors containing a water soluble polyvalent alcohol, a hydrotropic agent and as a printing assistants compound 01' the group consisting of arylsulphamino-anthraquinones, substitution products thereof and such reduction products of these compounds as still contain oxygen in the mesa-position.

17. The process which comprises printing cotton with printing colors derived from vat dyestuffs said colors containing as a printing assistant a compound of the group consisting of betaphenylsulphamino-anthraquinones, which may be substituted in the benzene nucleus by alkyl groups, and glycerine.

18. The process which comprises printing cotton with printing colors derived from vat dyestufis, said colors containing a hydrotropic agent and as a printing assistant a compound or the group consisting or beta-phenylsulphaminoanthraquinones, which may be substituted in the benzene nucleus by alkyl groups, and glycerine.

19. The process which comprises printing cotton with a printing color derived from 5.5'-dibenzoyldiamino 1 .1 dianthraquinonylamine carba zole, said color containing glycerine and as a printing assistant a compound of the group consisting of 2-para-toluenesulphaminoanthraquinone and 2.6-di-para-toluene-sulphaminoanthraquinone.

20. The process which comprises printing cotton with a printing color derived from 6.6'-diethoxy-2.2'-bis-thionaphthene indigo, said color containing xlycerine'and as a printing assistant 9. compound of the group consisting of 2-paratoluene sulphaminoanthraquinone and 2.6 di para-toluene-sulphaminoanthraquinone.

HERMANN BERTHOLD. go 

